US2267068A - Process fob producing ethers of - Google Patents

Process fob producing ethers of Download PDF

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US2267068A
US2267068A US2267068DA US2267068A US 2267068 A US2267068 A US 2267068A US 2267068D A US2267068D A US 2267068DA US 2267068 A US2267068 A US 2267068A
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thioammeline
parts
producing ethers
ethers
reaction
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom

Definitions

  • Our present invention relates to a Process producing ethers of thioammeline of the general formula:
  • R stands for a member of the group consisting of alkyl, cycloalkyl, aralkyl and aryl groups.
  • the process consists in treating thioammeline with an alkylating, cycloalkylating, aralkylating or arylating agent in an alkaline medium.
  • This reaction can be carried out in a smooth reaction with an excellent yield, a fact which could not be foreseen, since Rathke (Ber. vol, 20, page 1062 et seq.) could not succeed; the primarily formed mercaptides being decomposed in the moment of formation, so that he could only obtain a mixture of alkylmercaptans and ammeline.
  • the reaction can be stopped on the formation of thioethers, so that generally by acting on thioammeline with an alkylating, cycloalkylating, aralkylating or arylating agent the corresponding thioethers are obtained with an almost theoretical yield.
  • Di-thioethers are likewise obtainable. For instance by acting with ethylene bromide both bromine atoms are replaced by the mercapto radicle with the formation of the (ii-thioammeline-ethylene ether, a fact which is again in contradistinction to the publication of Rathke (loo. cit.), who could only replace on bromine atom, whereas the other one reacted with one imino group with ring closure.
  • the present ethers of thioammeline are mostly colorless crystalline powders, they are partly described in literature. According to A. W. Hofmann, (Ber. vol. 18, page 2755) they are formed by acting with alcoholic ammonia on sulfocyanuric acid alkylesters. In this case only a mixture of alkylthioammelines and considerable quantities of di-alkylmercapto-aminotriazines and melamine is formed, from which the desired product can only be isolated in a troublesome manner with a small yield.
  • the ethers of thioammeline are important intermediates for the manufactureof valuable artificial resins and assistants in @textile industry.
  • Example 1 143 parts of thioammeline are dissolved at about 30 to 40 in about 1800 parts of water and parts of a caustic soda solution of 40 B. Then 53 parts of anhydrous sodium carbonate and, while stirring and slightly cooling, 126 parts of dimethylsulfate are slowly added. The reaction mass is stirred until the colorless reaction product separates entirely. It is isolated and dried.
  • Example 2 To a solution of 143 parts of thioammeline in about 1800 parts of water and 240 parts of a of the formula:
  • CHF-CH3 N N HzN NHz being likewise a white powder of 184 to 185 by recrystallization melting point; the isobutylether being a white powder melting at 177 to 179.
  • Example 3 Into a solution of 214 parts of thioammeline in about 2700 parts of water and 180 parts of a caustic soda solution of 40 B. while'strongly stirring at to 189 parts of benzylchloride are added. After having stirred the mixture for some hours the thioammeline benzylether, which 25 has been formed as a colorless powder with an almost theoretical yield, is isolated. When recrystallized from alcohol it melts at 166 to 167.
  • Example 4 In the same manner as described in the foregoing examples a solution of 143 parts of thioammeline in about 1800 parts of water and 240 parts of a caustic soda solution of B. is decomposed with 94 parts of ethylene bromide at 35 to 40.
  • the isolated reaction product may be purified in acetic acid of strength, and the acetate, thus formed, may be decomposed by the action of a caustic soda solution.
  • Example 5 To a solution of 165 parts of thioammeline sodium salt in about 1800 parts of water and 120 parts of a caustic soda solution of 40 B.
  • R stands for a member of the group consisting of alkyl, cycloalkyl, aralkyl, and aryl groups, which process consists in treating thioammeline in an alkaline medium with a member of the group consisting of alkyl, cycloalkyl, aralkyl and aryl halides.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented Dec. 23, 1941 PROCESS FOR PRODUCING ETHERS or THIOAMMELINE Werner Zerweck, Frankfort-on-the-Main-Fechenheim, and Eduard Gofierj, Frankfort-onthe-Main, Germany, assignors, by mesne'assignments, to General Aniline & Film Corporation, New York, N. Y
ware
., a corporation of Dela- No Drawing. Application March 2, 1940, Serial No. 321,898. In Germany March 4, 1939 2 Claims.
Our present invention relates to a Process producing ethers of thioammeline of the general formula:
wherein R stands for a member of the group consisting of alkyl, cycloalkyl, aralkyl and aryl groups.
The process consists in treating thioammeline with an alkylating, cycloalkylating, aralkylating or arylating agent in an alkaline medium. This reaction can be carried out in a smooth reaction with an excellent yield, a fact which could not be foreseen, since Rathke (Ber. vol, 20, page 1062 et seq.) could not succeed; the primarily formed mercaptides being decomposed in the moment of formation, so that he could only obtain a mixture of alkylmercaptans and ammeline.
In contradistinction thereto, according to the present process by working in an alkaline medium the reaction can be stopped on the formation of thioethers, so that generally by acting on thioammeline with an alkylating, cycloalkylating, aralkylating or arylating agent the corresponding thioethers are obtained with an almost theoretical yield. Di-thioethers are likewise obtainable. For instance by acting with ethylene bromide both bromine atoms are replaced by the mercapto radicle with the formation of the (ii-thioammeline-ethylene ether, a fact which is again in contradistinction to the publication of Rathke (loo. cit.), who could only replace on bromine atom, whereas the other one reacted with one imino group with ring closure.
The present ethers of thioammeline are mostly colorless crystalline powders, they are partly described in literature. According to A. W. Hofmann, (Ber. vol. 18, page 2755) they are formed by acting with alcoholic ammonia on sulfocyanuric acid alkylesters. In this case only a mixture of alkylthioammelines and considerable quantities of di-alkylmercapto-aminotriazines and melamine is formed, from which the desired product can only be isolated in a troublesome manner with a small yield.
The ethers of thioammeline are important intermediates for the manufactureof valuable artificial resins and assistants in @textile industry.
In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in degrees centigrade.
Example 1 143 parts of thioammeline are dissolved at about 30 to 40 in about 1800 parts of water and parts of a caustic soda solution of 40 B. Then 53 parts of anhydrous sodium carbonate and, while stirring and slightly cooling, 126 parts of dimethylsulfate are slowly added. The reaction mass is stirred until the colorless reaction product separates entirely. It is isolated and dried.
Then with an excellent yield the thioammelinemethyl ether is obtained in a practically suificient degree of purity. When recrystallized from ethyl alcohol it melts at 267 to 268.
In the same manner by acting with diethyl sulfate on thioammeline the ethyl ether thereof which melts at 1'73 to 174 is obtained.
Example 2 To a solution of 143 parts of thioammeline in about 1800 parts of water and 240 parts of a of the formula:
S-UH
CHF-CH3 N N HzN= NHz being likewise a white powder of 184 to 185 by recrystallization melting point; the isobutylether being a white powder melting at 177 to 179.
When acting with cyclohexylbromide on thioammeline-sodium the cyclohexylether of the formula:
is obtained, being a White crystalline powder of 239-240 melting point.
Example 3 Into a solution of 214 parts of thioammeline in about 2700 parts of water and 180 parts of a caustic soda solution of 40 B. while'strongly stirring at to 189 parts of benzylchloride are added. After having stirred the mixture for some hours the thioammeline benzylether, which 25 has been formed as a colorless powder with an almost theoretical yield, is isolated. When recrystallized from alcohol it melts at 166 to 167.
Example 4 In the same manner as described in the foregoing examples a solution of 143 parts of thioammeline in about 1800 parts of water and 240 parts of a caustic soda solution of B. is decomposed with 94 parts of ethylene bromide at 35 to 40.
The isolated reaction product may be purified in acetic acid of strength, and the acetate, thus formed, may be decomposed by the action of a caustic soda solution. The di-thioammeline-ethyleneether of the formula:
s cHl -cms N N N N HzN- (ID-N132 HzN-( -NH:
50 thus obtained is a colorless powder melting at 264. It is not identical with the product of Rathke (Ber. d. Deutschen Chem. Ges. vol. 20, page 1063) obtained by acting with ethylene bromide on thioammeline in an alcoholic solution.
Example 5 To a solution of 165 parts of thioammeline sodium salt in about 1800 parts of water and 120 parts of a caustic soda solution of 40 B.
5 slowly at to 203 parts of 2.4-dinitro-chl0- robenzene are added and the reaction mixture is held at about 80 for some hours. The reaction product, separating as light yellow crystals, is filtered oil at 80 C., washed out with a warmed dilute caustic soda solution, then with water until v a neutral reaction and dried. The thioammeline dinitro phenylether of the formula:
. IITO,
. i r HzN-C CNH: melts at 243' C.
We claim: 1. Process for producing ethers of thioammeline of the general formula:
wherein R stands for a member of the group consisting of alkyl, cycloalkyl, aralkyl, and aryl groups, which process consists in treating thioammeline in an alkaline medium with a member of the group consisting of alkyl, cycloalkyl, aralkyl and aryl halides.
WERNER ZERWECIg.
EDUARD GOFFERJE.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415827A (en) * 1963-11-26 1968-12-10 Ciba Ltd Pesticidal triazinyl azides
US3497511A (en) * 1964-04-17 1970-02-24 Degussa Triazine compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415827A (en) * 1963-11-26 1968-12-10 Ciba Ltd Pesticidal triazinyl azides
US3497511A (en) * 1964-04-17 1970-02-24 Degussa Triazine compounds

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